US20050192374A1 - Dental resin composition, method of manufacture, and method of use thereof - Google Patents
Dental resin composition, method of manufacture, and method of use thereof Download PDFInfo
- Publication number
- US20050192374A1 US20050192374A1 US11/046,093 US4609305A US2005192374A1 US 20050192374 A1 US20050192374 A1 US 20050192374A1 US 4609305 A US4609305 A US 4609305A US 2005192374 A1 US2005192374 A1 US 2005192374A1
- Authority
- US
- United States
- Prior art keywords
- hydroxy
- meth
- acrylate
- alkyl
- composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 0 C1=CC=CC=C1.CC.CC.[5*]C(=C)(=O)CC(C)=O.[5*]C(=C)(C)(=O)=O Chemical compound C1=CC=CC=C1.CC.CC.[5*]C(=C)(=O)CC(C)=O.[5*]C(=C)(C)(=O)=O 0.000 description 13
- CPQVOFPSOHBZAV-UHFFFAOYSA-N CC(C)=O.CCC(=O)CC.CCC(C)=O.CCC(C)=O Chemical compound CC(C)=O.CCC(=O)CC.CCC(C)=O.CCC(C)=O CPQVOFPSOHBZAV-UHFFFAOYSA-N 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N CCC(C)=O Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- BMBNMXXPSHKOGL-UHFFFAOYSA-N C=C=C(C)OOCCOC(=O)CCCCCOC(=O)C1=CC(C(=O)O)=C(C(=O)OCCCCCC(=O)OCCOOC(C)=C=C)C=C1C(=O)O.C=C=C(C)OOCCOC(=O)CCCCCOC(=O)C1=CC(C(=O)OCCCCCC(=O)OCCOOC(C)=C=C)=C(C(=O)O)C=C1C(=O)O Chemical compound C=C=C(C)OOCCOC(=O)CCCCCOC(=O)C1=CC(C(=O)O)=C(C(=O)OCCCCCC(=O)OCCOOC(C)=C=C)C=C1C(=O)O.C=C=C(C)OOCCOC(=O)CCCCCOC(=O)C1=CC(C(=O)OCCCCCC(=O)OCCOOC(C)=C=C)=C(C(=O)O)C=C1C(=O)O BMBNMXXPSHKOGL-UHFFFAOYSA-N 0.000 description 1
- JFPOJYQHXMJXND-UHFFFAOYSA-N C=C=C(C)OOCCOC(=O)CCCCCOC(=O)C1=CC(C(=O)O)=C(C(=O)OCCOOC(C)=C=C)C=C1C(=O)O.C=C=C(C)OOCCOC(=O)CCCCCOC(=O)C1=CC(C(=O)OCCOOC(C)=C=C)=C(C(=O)O)C=C1C(=O)O Chemical compound C=C=C(C)OOCCOC(=O)CCCCCOC(=O)C1=CC(C(=O)O)=C(C(=O)OCCOOC(C)=C=C)C=C1C(=O)O.C=C=C(C)OOCCOC(=O)CCCCCOC(=O)C1=CC(C(=O)OCCOOC(C)=C=C)=C(C(=O)O)C=C1C(=O)O JFPOJYQHXMJXND-UHFFFAOYSA-N 0.000 description 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N c1ccccc1 Chemical compound c1ccccc1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/50—Preparations specially adapted for dental root treatment
- A61K6/54—Filling; Sealing
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/30—Compositions for temporarily or permanently fixing teeth or palates, e.g. primers for dental adhesives
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
- A61K6/884—Preparations for artificial teeth, for filling teeth or for capping teeth comprising natural or synthetic resins
- A61K6/887—Compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
Definitions
- This invention relates to dental resin compositions comprising polymerizable (meth)acrylate resins, their method of manufacture, and the use of such resins for restorative dentistry, including dental adhesives, dental cements, dental filling materials, root canal sealants, crown and bridge materials, and the like.
- materials used for dental restorations have principally comprised acrylate or methacrylate resins.
- Resinous materials of this type are disclosed, for example, in U.S. Pat. No. 3,066,112 to Bowen, No. 3,194,784 to Bowen, and No. 3,926,906 to Lee et al.
- An especially important methacrylate monomer is the condensation product of bisphenol A and glycidyl methacrylate, 2,2′-bis[4-(3-methacryloxy-2-hydroxy propoxy)-phenyl]-propane (“BisGMA”).
- BisGMA may be synthesized from the diglycidyl ether of bisphenol A and methacrylic acid (see, e.g., U.S. Pat. No. 3,066,112 to Bowen).
- compositions are useful for a variety of dental treatments and restorative functions including crown and bridge materials, fillings, adhesives, sealants, luting agents or cements, denture base materials, orthodontic materials and sealants, and other dental restorative materials. Despite their suitability for their intended purposes, however, many of these materials have shrinkages of about two to about four percent by volume upon polymerization.
- composition comprising a polymerizable (meth)acrylate of general structure I: wherein
- a method of manufacturing a composition comprising a polymerizable (meth)acrylate comprises reacting a hydroxy-containing (meth)acrylate monomer of structure II: wherein
- a method of making a dental restoration comprises applying to a site to be restored a composition comprising the above-described polymerizable (meth)acrylate of general structure I, and polymerizing the (meth)acrylate.
- the FIGURE is a graph illustrating cure time after ageing of a composition in accordance with the present invention and a control.
- the polymerizable (meth)acrylates described herein are useful as dental resins and possess improved properties over existing dental resins, and correspondingly enhance the properties of dental restorative materials prepared from such resins.
- the polymerizable (meth)acrylates provide excellent bonding strength between a dental substrate (dentin, enamel, or other tooth structure) and the dental restorative material made from the polymerizable (meth)acrylate.
- dental restorative materials prepared from the polymerizable (meth)acrylates exhibit reduced shrinkage upon polymerization to provide a better seal between the dental restoration and the repaired tooth.
- an improved dental resin is of formula I:
- n 0, 1, 2, or 3
- q is 0 or 1
- A is an anhydride group
- a is 0 or 1.
- the anhydride group (—C(O)—O—C(O)—) is linked via its two carbon atoms to two ortho carbons of the phenyl ring.
- a is 0.
- n is preferably 1 or 2.
- R 1 , R 2 , R 3 , and R 4 are each independently hydrogen, hydroxy, C 1 -C 12 alkyl, C 1 -C 12 perhaloalkyl, C 1 -C 12 alkoxy, C 1 -C 12 perhaloalkoxy, C 2 -C 12 alkenyl, C 2 -C 12 alkynyl, (C 1 -C 6 alkyl)-O-(C 1 -C 6 alkylene), or hydroxy(C 1 -C 6 alkylene), wherein x and y are each independently an integer from 1 to 10.
- R 1 , R 2 , R 3 , and R 4 are each independently hydrogen, hydroxy, or C 1 -C 12 alkyl, and x and y is each independently an integer from 1 to 6. More preferably R 1 , R 2 , R 3 , and R 4 is each independently hydrogen or C 1 -C 6 alkyl.
- R 5 in structure I is a hydrogen or methyl group, and is preferably a methyl group.
- M in structure I is a carbonyl-containing group, in particular wherein G and J are each independently oxygen or NR 6 , wherein R 6 is hydrogen or C 1 -C 6 alkyl; and m is 1, 2, 3, or 4.
- M is wherein G is oxygen, and m is 1, 2, or 3.
- a is 1, n+m+q is 1, 2, 3, or 4, and when a is 0, n+m+is 1, 2, 3, 4, 5, or 6.
- W in structure I is a hydrocarbyl linking group having a valency corresponding to z, the number of (meth)acrylate groups, plus one.
- W may be aromatic or aliphatic. Suitable aromatic groups are phenyl and napthyl, and suitable aliphatic groups are C 1 -C 12 alkyl, cycloalkyl, alkenyl, or alkynyl groups.
- the improved dental resin composition comprises a polymerizable (meth)acrylate of the general structure III:
- n, q, M, A, and a are as described above.
- a is 0 and n is 0 or 1.
- R 1 , R 2 , R 3 , R 4 , R 5 , x, and y are as described above.
- R 6 and R 7 are each independently hydrogen, hydroxy, C 1 -C 12 alkyl, C 1 -C 12 perhaloalkyl, C 1 -C 12 alkoxy, C 1 -C 12 perhaloalkoxy, C 2 -C 12 alkenyl, C 2 -C 12 alkynyl, (C 1 -C 6 alkyl)-O-(C 1 -C 6 alkylene), or hydroxy(C 1 -C 6 alkylene), wherein z is an integer of 1 to 5, preferably 1 to 3.
- R 1 , R 2 , R 3 , R 4 , R 6 , and R 7 are each independently hydrogen, hydroxy, or C 1 -C 12 alkyl, and x and y is each independently an integer from 1 to 6. More preferably R 1 , R 2 , R 3 , R 4 , R 6 , and R 7 is each independently hydrogen or C 1 -C 6 alkyl.
- the polymerizable (meth)acrylate (I) may be synthesized, for example, from the reaction of a hydroxy-containing (meth)acrylate monomer and an aromatic compound comprising anhydride or carboxylic acid functionality or their synthetic equivalents (e.g., a carboxylic acid halide, for example chloride).
- An exemplary synthetic preparation includes the reaction of one mole of an aromatic anhydride, for example benzenetetracarboxylic acid dianhydride (BTAD) or pyromellitic dianhydride (PMDA), with two moles of a hydroxy-containing (meth)acrylate, for example caprolactone 2-(methacryloyloxy)ethyl ester (CLMA, or 2-(6-hydroxy-1-oxo-hexyloxy)ethyl methacrylate), at elevated temperature in the presence of a catalyst, for example a catalytic amount of stannous ethylhexanoate (SEH).
- a catalyst for example a catalytic amount of stannous ethylhexanoate (SEH).
- SEH stannous ethylhexanoate
- Any number of the remaining carboxylic acid groups may further be reacted with an additional hydroxy-containing (meth)acrylate monomer to form a modified polymerizable (meth)acrylate.
- the ratio of moles of hydroxy-containing (meth)acrylate monomer to moles of anhydride or carboxylic acid, as well as the reaction conditions and/or starting materials, may be varied to provide a wide range of polymerizable (meth)acrylate products.
- Exemplary aromatic compounds comprising anhydride functionality, carboxylic acid functionality, or a combination thereof useful to prepare the polymerizable (meth)acrylate of structure I include BTAD, PMDA, all isomers of benzenetetracarboxylic acid, preferably benzene-1,2,4,5-tetracarboxylic acid, 1,3-dihydro-1,3-dioxoisobenzofuran-4,5-dicarboxylic acid, 1,3-dihydro-1,3-dioxoisobenzofuran-5,6-dicarboxylic acid, trimellitic anhydride, trimellitic acid, terephthalic acid, phthalic acid, phthalic anhydride, benzoic acid, 4′-(4,4′-isopropylidenediphenoxy)-bis(phthalic anhydride) (IBA), and the like.
- BTAD benzene-1,2,4,5-tetracarboxylic acid
- Preferred aromatic anhydride and/or carboxylic acid compounds include BTAD, 1,3-dihydro-1,3-dioxoisobenzofuran-4,5-dicarboxylic acid, PMDA, benzene-1,2,4,5-tetracarboxylic acid, 1,3-dihydro-1,3-dioxoisobenzofuran-5,6-dicarboxylic acid, trimellitic anhydride, and trimellitic acid.
- Suitable hydroxy-containing (meth)acrylate monomers include, for example, those of the general structure II: wherein R 1 , R 2 , R 3 , R 4 , x, y, and M are as described above.
- a preferred hydroxy-containing (meth)acrylate monomer is a compound according to structure II wherein R 1 , R 2 , R 3 , and R 4 are each hydrogen; x and y are each independently an integer from 1 to 5; M is wherein G is oxygen; and R 5 is hydrogen or methyl, more preferably methyl.
- suitable hydroxy-containing (meth)acrylate monomers according to structure II include CLMA, caprolactone 2-(acryloyloxy) ethyl ester, and 3-hydroxy-1-oxopropyl (meth)acrylate.
- the most preferred hydroxy-containing (meth)acrylate monomers are CLMA and caprolactone 2-(acryloyloxy)ethyl ester. Mixtures of two or more different hydroxy-containing (meth)acrylates of formula II may also be used.
- CLMA may be prepared by the condensation of ⁇ -caprolactone and 2-hydroxyethyl methacrylate.
- isocyanate alkyl (meth)acrylate e.g., isocyanate methyl (meth)acrylate
- a suitably monoprotected amino alcohol or dialcohol followed by deprotection to result in a hydroxy-containing methacrylate comprising urea or carbamate functionality.
- the ratio of moles of hydroxy-containing (meth)acrylate monomer to the moles of aromatic anhydride, carboxylic acid, or its equivalent may be selected to obtain a resin that provides desired properties of adhesion and reduced shrinkage upon polymerization.
- the ratio of moles of hydroxy-containing (meth)acrylate monomer to moles of aromatic anhydride and/or carboxylic acid may be about 0.1 to about 5, preferably about 0.5 to about 4, more preferably about 0.75 to about 3, and yet more preferably about 1 to about 2.
- the catalyst used to prepare the polymerizable (meth)acrylate according to the general structure (I) may be selected from metal organic catalysts comprising tin or titanium.
- tin-containing catalysts are dibutyltin dilaurate, dibutyltin maleate, dibutyltin diacetate, dioctyltin maleate, dibutyltin phthalate, stannous octoate, stannous naphthenate, stannous stearate, stannous 2-ethyl hexanoate, dibutyltin diacetylacetonate, dibutyltin oxide, and combinations comprising at least one of the foregoing tin based catalysts.
- titanium-based catalysts are tetrabutyl titanate, tetrapropyl titanate, tetraisopropyl titanate, triethanolamine titanate, titanium tetraacetylacetonate, and combinations comprising at least one of the foregoing titanium based catalysts.
- the preferred catalysts are stannous octoate or stannous 2-ethyl hexanoate.
- the catalyst in an amount of about 0.10 to about 10 mole percent based on the total moles of the reactant mixture. Within this range it is generally desirable to utilize the catalyst in an amount about 1 to about 8, preferably about 2 to about 7, and most preferably about 3 to about 6 mole percent based on the total moles of the reactants.
- the polymerizable (meth)acrylate of structure (I) may be formed by reaction of an aromatic compound comprising anhydride functionality, carboxylic acid functionality, or a combination thereof with a mixture comprising a hydroxy-containing (meth)acrylate of formula II and an additional, different hydroxy-containing methacrylate of formula IV: wherein W and R 5 are as defined above.
- Exemplary suitable hydroxy-containing (meth)acrylate monomers of this type include compounds comprising two or more (meth)acrylate groups, for example, glyceryl di(meth)acrylate, glycerol di(meth)acrylate, trimethylolpropane di(meth)acrylate; pentaerythritol tri(meth)acrylate and the like.
- the different hydroxy-containing (meth)acrylate is of structure V: wherein R 6 and R 7 are each independently hydrogen, hydroxy, C 1 -C 12 alkyl, C 1 -C 12 perhaloalkyl, C 1 -C 12 alkoxy, C 1 -C 12 perhaloalkoxy, C 2 -C 12 alkenyl, C 2 -C 12 alkynyl, (C 1 -C 6 alkyl)-O-(C 1 -C 6 alkylene), or hydroxy(C 1 -C 6 alkylene); z is an integer from 1 to 10; and R 5 is hydrogen or methyl.
- the additional hydroxy (meth)acrylate according to structure V comprises a compound wherein R 6 and R 7 are each independently hydrogen, C 1 -C 12 alkyl, or hydroxy; and z is an integer from 1 to 10; and R 5 is methyl.
- exemplary compounds include 2-hydroxyethyl methyacrylate (HEMA), 2-hydroxyethyl acrylate, hydroxypropyl (meth)acrylate, and glyceryl mono(meth)acrylate. Mixtures of the additional monomers may also be used.
- the ratio of the moles of additional hydroxy-containing (meth)acrylate monomer to moles of anhydride and/or carboxylic acid of structure I, monomer II, and the additional monomer(s) may be selected to provide a modified polymerizable (meth)acrylate possessing desired properties.
- the ratio of moles of additional hydroxy-containing (meth)acrylate monomer to moles of anhydride and/or carboxylic acid groups of structure (I) may be about 0.1:1 to about 5:1, preferably about 0.5:1 to about 4:1, more preferably about 0.75:1 to about 3:1, and yet more preferably about 1:1 to about 2:1.
- An exemplary polymerizable (meth)acrylate in accordance with the present invention is the reaction product of BTAD with CLMA, having structures VIa and/or VIb as follows:
- Another exemplary polymerizable (meth)acrylate in accordance with the present invention is the reaction product of BTAD with mixtures of CLMA and HEMA, having the structure (VIIa) and/or (VIIb) as follows:
- the polymerizable (meth)acrylates may be used alone or in combination with other co-polymerizable, ethylenically unsaturated monomers and/or oligomers.
- co-polymerizable, ethylenically unsaturated monomers and/oligomers containing carboxylic acid(s), phosphoric acid(s), sulfonic acid(s) or their anhydride(s) may be utilized in combination with the polymerizable (meth)acrylates of this invention.
- Mixtures comprising the polymerizable (meth)acrylate and other components such as polymerization initiators, additives, and fillers may be prepared to form dental materials suitable for use as dental adhesives, dental cements, dental filling materials, root canal sealing/filling materials, and/or other dental restorative materials such as crown and bridge materials, provisional crown and bridge materials, and the like. It is generally desirable to use the polymerizable (meth)acrylate in an amount of about 1 to about 99 weight percent based on the total weight of the dental restorative material.
- the polymerizable (meth)acrylate in an amount of about 10 to about 95 weight percent, preferably about 30 to about 90 weight percent, and most preferably about 50 to about 80 weight percent based on the total weight of the dental restorative material.
- Known viscous resins may be used in combination with the polymerizable (meth)acrylate to provide a dental restorative material.
- Non-limiting examples include polyurethane dimethacrylates (PUDMA), diurethane dimethacrylates (DUDMA), and/or the polycarbonate dimethacrylate (PCDMA) disclosed in U.S. Pat. Nos. 5,276,068 and 5,444,104 to Waknine, which is the condensation product of two parts of a hydroxyalkylmethacrylate and 1 part of a bis(chloroformate).
- Another advantageous resin having lower water sorption characteristics is an ethoxylated bisphenol A dimethacrylate (EBPDMA) as disclosed in U.S. Pat. No. 6,013,694 to Jia, et al.
- Still another useful resin material is disclosed in U.S. Pat. No. 6,787,629 to Jia, et al.
- An especially useful methacrylate resin is BisGMA.
- Diluent monomers may be used to increase the surface wettability of the composition and/or to decrease the viscosity of the polymerization medium.
- Suitable diluent monomers include those known in the art such as hydroxyalkyl (meth)acrylates, for example 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate; ethylene glycol (meth)acrylates, including ethylene glycol methacrylate, diethylene glycol methacrylate, tri(ethylene glycol) dimethacrylate and tetra(ethylene glycol) dimethacrylate; and diol dimethacrylates such as 1,4-butanediol di(meth)acrylate, dodecane diol di(meth)acrylate, or 1,6-hexanediol di(meth)acrylate, particularly 1,6-hexanediol dimethacrylate (HDDMA).
- Suitable monomers include polyethylene glycol mono(meth)acrylate; glycerol di(meth)acrylate; trimethylolpropane di(meth)acrylate; pentaerythritol tri(meth)acrylate; the (meth)acrylate of phenyl glycidyl ether; and the like.
- Tri(ethylene glycol) dimethacrylate (TEGDMA) is particularly preferred.
- Diluent monomers or viscous resins when present, are incorporated into the dental restorative materials in an amount of about 1 to about 70 weight percent of the total dental restorative material.
- the optional filler system may comprise one or more of the inorganic fillers currently used in dental composite materials.
- Preferred fillers include those, which are capable of being covalently bonded to the polymerizable (meth)acrylate matrix itself or to a coupling agent (e.g., silanes) that is covalently bonded to both.
- suitable filling materials include but are not limited to, silica, quartz, strontium silicate, strontium borosilicate, lithium silicate, lithium alumina silicate, amorphous silica, ammoniated or deammoniated calcium phosphate, tricalcium phosphate alumina, zirconia, tin oxide, titania and combinations comprising at least one of the foregoing fillers.
- inorganic filling materials and methods of preparation thereof are known in the art, as disclosed in U.S. Pat. No. 4,544,359 and No. 4,547,531 to Waknine, pertinent portions of which are incorporated herein by reference.
- Organic-inorganic fillers of POSSTM Hybrid Plastics
- Other organic-inorganic fillers such as zirconium methacrylate and zirconium dimethacrylate under the codes of CXZR050 and CXZR051 (Gelest, Inc.) can also be used.
- Suitable high refractive index filler materials such as high refractive index silica glass fillers; calcium silicate based fillers such as apatites, hydroxyapatites or modified hydroxyapatite compositions may also be used.
- inert, non-toxic radiopaque materials such as bismuth oxide (Bi 2 O 3 ), bismuth oxychloride, zirconium oxide, barium sulfate, and bismuth subcarbonate in micro- or nano scaled sizes may be used.
- fibrous fillers such as those disclosed in U.S. Pat. Nos. 6,013,694, 6,403,676 and 6,270,562 to Jia and Jia et al. may also be used.
- Suitable fillers have particle sizes of about 0.01 to about 5.0 micrometers, and may further comprise bound or unbound silicate colloids of about 0.001 to about 0.2 micrometers. These additional fillers may also be treated with a silane-coupling agent to increase adhesion with the polymerizable, (meth)acrylate.
- silane treated fumed silica based on Aerosil A200 can be obtained from Degussa Corp under the names of Aerosil R711 and R7200.
- the amount of total filler system in the dental restorative material can vary from about 1 to about 90 weight percent based on the total weight of the dental restorative material.
- the amount used is determined by the requirements of the particular application.
- crown and bridge materials generally comprise about 60 to about 90 weight percent filler
- luting cements comprise about 20 to about 80 weight percent filler
- sealants generally comprise about 1 to about 20 weight percent filler
- adhesives generally comprise about 1 to about 30 weight percent filler
- restorative materials comprise about 50 to about 90 weight percent filler, with the remainder in all cases being the polymerizable (meth)acrylate and other optionally added resins.
- the polymerizable (meth)acrylate may be used together with a curing system, which generally includes polymerization initiators; polymerization accelerators; ultraviolet light absorbers; antioxidants; and other additives known in the art.
- a curing system which generally includes polymerization initiators; polymerization accelerators; ultraviolet light absorbers; antioxidants; and other additives known in the art.
- Suitable polymerization initiators are those initiators that can be utilized in UV-activated cure or visible light-activated cure compositions.
- visible light-curable compositions employ light-sensitive compounds, including but not being limited to benzil, benzoin, benzoin methyl ether, DL-camphorquinone (CQ), and benzil diketones.
- Either UV-activated cure or visible light-activated cure (approximately 230 to 750 nanometer) is acceptable.
- the amount of photoinitiator is selected according to the curing rate desired. A minimal catalytically effective amount is generally about 0.01 weight percent of the total dental resin composition, and will lead to a slower cure.
- the total dental resin composition is the total weight of the polymerizable (meth)acrylate and other resinous materials, such as for example, resinous diluents, which are used in the dental restorative material.
- the dental restorative material may be formulated as a self-curing system.
- Self-curing dental composite materials will generally contain free radical polymerization initiators such as, for example, a peroxide in an amount of about 0.01 to about 1.0 weight percent of the total resin dental composite material.
- free radical initiators are lauryl peroxide, tributyl hydroperoxide and, more particularly benzoyl peroxide (BPO).
- Polymerization accelerators suitable for use are the various organic tertiary amines well known in the art.
- the tertiary amines are generally (meth)acrylate derivatives such as dimethylaminoethyl methacrylate and, particularly, diethylaminoethyl methacrylate (DEAEMA) in an amount of about 0.05 to about 0.5 weight percent of the total dental restorative material.
- DEAEMA diethylaminoethyl methacrylate
- the tertiary amines are generally aromatic tertiary amines, preferably tertiary aromatic amines such as ethyl 4-(dimethylamino)benzoate (EDMAB), 2-[4-(dimethylamino)phenyl]ethanol, N,N-dimethyl-p-toluidine (DMPT), and bis(hydroxyethyl)-p-toluidine (DHEPT).
- EDMAB ethyl 4-(dimethylamino)benzoate
- DMPT N,N-dimethyl-p-toluidine
- DHEPT bis(hydroxyethyl)-p-toluidine
- Such accelerators are generally present in an amount of about 0.5 to about 4.0 weight percent of the total dental restorative material.
- an ultraviolet absorber in an amount of about 0.05 to about 5.0 weight percent of the total dental restorative material.
- Such UV absorbers are particularly desirable in the visible light-curable dental restorative materials in order to avoid discoloration of the resin from incident ultraviolet light.
- Suitable UV absorbers are the various benzophenones, particularly UV-5411 available from American Cyanamid Company.
- the polymerizable (meth)acrylate is prepared by reacting an aromatic compound comprising anhydride and/or carboxylic acid functionality with a hydroxy-containing (meth)acrylate monomer in the presence of a catalyst.
- the resulting polymerizable (meth)acrylate is then formulated into a dental restorative material by mixing with the filler system and the curing system.
- the dental restorative material is then applied to the tooth to be repaired, and cured.
- the dental restorative material may be formulated as a two-part system, wherein the first part can comprise the polymerizable (meth)acrylate and the filler system.
- the second part can comprise the curing system and optional diluent monomers.
- the two parts are metered out and then mixed using a spatula.
- the cure may be initiated through the use of UV light or by raising the temperature of the mixture.
- the dental restorative material thus obtained is then placed in the tooth to be restored after the tooth is appropriately prepared.
- (meth)acrylate is intended to encompass both acrylate and methacrylate groups. All ranges disclosed herein are inclusive and combinable. In addition, all patents are incorporated by reference in their entirety.
- BTAD 1,2,4,5-benzenetetracarboxylic dianhydride
- CLMA 2-(caprolactone)ethyl methacrylate
- HEMA 2-hydroxyethyl methacrylate
- SEH tin(II) 2-ethylhexanoate
- the synthesized resins BTAD-CLMA and BTAD-CLMA-HEMA were each mixed with a conventional resin and diluent (PUDMA and HDDMA)in a weight ratio of 50/40/10. Quantities of 0.2 wt % CQ and 0.4 wt % EDMAB were added as photoinitiators. The samples were cured for a total four minutes using visible light with CureLiteTM Plus curing box (Pentron Corp.) Samples were then trimmed and stored in water at 37° C. for 24 hours before testing.
- Resin 1 and Resin 2 were further used to make a light-curable dental composite with the addition of treated silica filler (R7200 from Degussa), a sol-gel processed zirconium silicate filler as disclosed in U.S. Patent Publ. No. 2003/0125444 A1 and Schott glass filler (Schott 8235, available from Schott Electronic Packaging Gmbh, Germany).
- treated silica filler R7200 from Degussa
- a sol-gel processed zirconium silicate filler as disclosed in U.S. Patent Publ. No. 2003/0125444 A1 and Schott glass filler (Schott 8235, available from Schott Electronic Packaging Gmbh, Germany).
- the same filler combination and loading (78 wt. % filler) were used in to form Composite 1 from Resin 1 and Composite 2 from Resin 2.
- the composites were tested and the MOR results are shown in Table 2.
- Samples of self-curing compositions with and without BTAD-CLMA in the catalyst part were prepared to evaluate the effect BTAD-CLMA on cure.
- the samples, designated SC1 and SC2 were each formed from two paste components, a catalyst paste and a base paste.
- the catalyst past and base paste were each prepared from a resin and a filler that have the compositions shown in Table 3.
- the SC1 catalyst resin contains 10 wt. % of BTAD-CLMA, while SC2 does not.
- Other components for samples SC1 and SC2 are similar.
- Catalyst paste 1 and Catalyst paste 2 were mixed in 1:1 wt. ratio with the base paste.
- Base resin catalyst Base resin: DHEPT 1.5 wt %, BHT and base DHEPT 1.5 wt %, BHT 0.05 wt % in EBPADMA pastes 0.05 wt % in EBPADMA Paste
- Catalyst paste 1 Catalyst paste 2: Compo- Catalyst resin 1: 35 Catalyst resin 2: 35 nents wt % wt %
- Filler 65 wt % of Filler: 65 wt % of treated silica and treated silica and glass filler glass filler
- Base paste Base paste: Base resin: 30 wt % Base resin: 30 wt % Filler: 70 wt % of Filler: 70 wt % of treated silica and treated silica and glass filler, barium glass filler, barium sulfate and calcium sulfate and calcium hydroxide hydroxide
- FIGURE shows the stability test results of samples SC1 and SC2 at room temperature for 8 weeks.
- Sample SC1 shows stable gel time and setting time during the 8 weeks storage at room temperature, but sample SC2 shows increasing gel time and setting time.
- the present polymerizable (meth)acrylates resins can be used to prepare a light curable, one-component adhesive composite for tooth restorations, wherein the composites can be used without a separate dental bonding procedure prior to a the application of the material. Such procedures can be time-consuming, and their elimination is highly advantageous.
- compositions per Components Function in the composition hundred BTAD-CLMA-HEMA Resin matrix component and 20 adhesion promoter HEMA A co-polymerizable resin 20 diluent and hydrophilicity modifier for the composition
- compositions have a flowable consistency, which allows delivery of the composite through a cannula, for example a needle tip directly onto a tooth surface. Again, it has been found that a separate bonding procedure, i.e. an additional bonding adhesive is not necessary.
- These compositions may be used, for example, for cementing a veneer, lining a tooth cavity underneath a regular dental restorative composite, sealing a root canal coronal end, placing as a direct tooth filling, securing an orthodontic bracket, or the like.
- the present polymerizable (meth)acrylates resins can be used to prepare self and/or dual-curable two-component composites suitable for use as an adhesive luting cement, a core build-up material, a root canal filling/sealing material, or the like. In an advantageous feature, use of a separate bonding procedure before using the composite material is not necessary.
- An exemplary composition is illustrated in the table below.
- the working time and setting time of the above composition is about three minutes and four and half minutes, respectively, when the base and catalyst is mixed in 1:1 ratio by volume and the material is not subject to a second curing process.
- dual-cure mode when the material, upon mixing the base and catalyst, is subject to a dental visible light-curing source, the mass of the material will harden immediately upon the photoinitiation.
- the Table below shows the results of cementation/bonding tests of the present polymerizable (meth)acrylates resin composite compositions between dentin and a ceramic (3GTM ceramic material, Pentron Corp., Wallingford, Conn.).
- the bonding test method was as follows:
- 3GTM ceramic rods were fabricated with a dental porcelain furnace according to the ceramic firing temperature and conditions of the product.
- the 3GTM ceramic rods used for the bonding test have final dimensions of about 3.2 mm diameter and 6-8 mm length, on which one end of the rod was sandblasted, cleaned and then silane treated as per the product instructions. The treated end will be contacting the bonding cement as in a tooth restoration.
- Each test group contains 5 samples.
- Teeth samples were prepared to expose the dentin and then the teeth were mounted with an acrylic material leaving the dentin exposed, which were then subject to sand paper grinding under wet condition to have a same surface pattern for all the test groups.
- the cement materials were mixed according to the product instructions and applied onto the prepared, briefly dried tooth surface.
- the ceramic rod was then seated onto the cement surface under a 500 gram load with the aid of a BenCor Multi-test device (Danville Engineering, CA).
- TM resin 0.3 (1.2) A paste-paste conven- cement, shade A2 tional methacrylate resin cement as a control and used without a separated bonding procedure before the applica- tion of the cement available from Pen- tron Corp., Walling- ford, CT. Lute-It TM resin 14.8 (1.6) Before apply the cement, shade A2, mixed cement onto used in conjunc- the tooth surface, a tion with Bond-1 TM separated bonding dental adhesive procedure is per- formed per the in- struction of the Bond-1 TM dental bonding system, available from Pentron Corp., Wallingford, CT.
Abstract
wherein A is an anhydride; a is 0 or 1; n is 0, 1, 2, or 3; R1, R2, R3, and R4 are each independently hydrogen, hydroxy, C1-C12 alkyl, C1-C12 perhaloalkyl, C1-C12 alkoxy, C1-C12 perhaloalkoxy, C2-C12 alkenyl, C2-C12 alkynyl, (C1-C6 alkyl)-O-(C1-C6 alkylene), or hydroxy(C1-C6 alkylene); x and y are each independently an integer of 1 to 10; z is an integer of 1 to 5; R5 is hydrogen or methyl; M is
wherein G and J are each independently O or NR6, wherein R6 is hydrogen or C1-C6 alkyl; m is 1, 2, 3, or 4; W is an organic group having the valency of z+1; and q is 0 or 1; and further wherein when a is 1, n+m+q is 1, 2, 3, or 4, and when a is 0, n+m+q is 1, 2, 3, 4, 5, or 6. The composition finds use as a dental resin.
Description
- This application claims the benefit of U.S. Provisional Patent Application Ser. No. 60/540,148 filed Jan. 29, 2004.
- This invention relates to dental resin compositions comprising polymerizable (meth)acrylate resins, their method of manufacture, and the use of such resins for restorative dentistry, including dental adhesives, dental cements, dental filling materials, root canal sealants, crown and bridge materials, and the like.
- In recent years, materials used for dental restorations have principally comprised acrylate or methacrylate resins. Resinous materials of this type are disclosed, for example, in U.S. Pat. No. 3,066,112 to Bowen, No. 3,194,784 to Bowen, and No. 3,926,906 to Lee et al. An especially important methacrylate monomer is the condensation product of bisphenol A and glycidyl methacrylate, 2,2′-bis[4-(3-methacryloxy-2-hydroxy propoxy)-phenyl]-propane (“BisGMA”). Alternatively, BisGMA may be synthesized from the diglycidyl ether of bisphenol A and methacrylic acid (see, e.g., U.S. Pat. No. 3,066,112 to Bowen).
- Because the wear and abrasion characteristics and the overall physical, mechanical, and optical properties of these unfilled acrylic resinous materials is poor, and because acrylic resin systems exhibit high coefficients of thermal expansion relative to the coefficient of thermal expansion of the tooth structure, these substances by themselves are less than satisfactory. In particular, the disparity in thermal expansion coupled with high shrinkage upon polymerization results in poor marginal adaptability, and ultimately leads to secondary decay. Composite dental restorative materials containing acrylate or methacrylate resins and fillers were thus developed. The fillers are generally inorganic materials based on silica, silicate based glasses, or quartz. These filled compositions are useful for a variety of dental treatments and restorative functions including crown and bridge materials, fillings, adhesives, sealants, luting agents or cements, denture base materials, orthodontic materials and sealants, and other dental restorative materials. Despite their suitability for their intended purposes, however, many of these materials have shrinkages of about two to about four percent by volume upon polymerization.
- There accordingly remains a need in the art for dental resin materials that have good bonding adhesion to a dental substrate and minimal shrinkage upon polymerization without sacrificing other advantageous physical properties.
-
-
- A is an anhydride;
- a is 0 or 1;
- n is 0, 1, 2, or 3;
- R1, R2, R3, and R4 are each independently hydrogen, hydroxy, C1-C12 alkyl, C1-C12 perhaloalkyl, C1-C12 alkoxy, C1-C12 perhaloalkoxy, C2-C12 alkenyl, C2-C12 alkynyl, (C1-C6 alkyl)-O-(C1-C6 alkylene), or hydroxy(C1-C6 alkylene);
- x and y are each independently an integer of 1 to 10;
- z is an integer of 1 to 5;
- R5 is hydrogen or methyl;
- wherein G and J are each independently O or NR6, wherein R6 is hydrogen or C1-C6 alkyl;
- m is 1, 2, 3, or 4;
- W is an organic group having the valency of z+1; and
- q is 0 or 1,
and further wherein when a is 1, n+m+q is 1, 2, 3, or 4, and when a is 0, n+m+q is 1, 2, 3, 4, 5, or 6.
-
-
- R1, R2, R3, and R4 are each independently hydrogen, hydroxy, C1-C12 alkyl, C1-C12 perhaloalkyl, C1-C12 alkoxy, C1-C12 perhaloalkoxy, C2-C12 alkenyl, C2-C12 alkynyl, (C1-C6 alkyl)-O-(C1-C6 alkylene), or hydroxy(C1-C6 alkylene);
- x and y are each independently an integer from 1 to 10;
- R5 is hydrogen or methyl; and
- wherein G and J are each independently O or NR6, wherein R6 is hydrogen or C1-C6 alkyl,
with an aromatic compound comprising anhydride functionality, carboxylic acid functionality, or a combination thereof
- In yet another embodiment, a method of making a dental restoration comprises applying to a site to be restored a composition comprising the above-described polymerizable (meth)acrylate of general structure I, and polymerizing the (meth)acrylate.
- The FIGURE is a graph illustrating cure time after ageing of a composition in accordance with the present invention and a control.
- The polymerizable (meth)acrylates described herein are useful as dental resins and possess improved properties over existing dental resins, and correspondingly enhance the properties of dental restorative materials prepared from such resins. For instance, the polymerizable (meth)acrylates provide excellent bonding strength between a dental substrate (dentin, enamel, or other tooth structure) and the dental restorative material made from the polymerizable (meth)acrylate. Additionally, dental restorative materials prepared from the polymerizable (meth)acrylates exhibit reduced shrinkage upon polymerization to provide a better seal between the dental restoration and the repaired tooth.
-
- In structure I, n is 0, 1, 2, or 3, q is 0 or 1, A is an anhydride group, and a is 0 or 1. As is known, the anhydride group (—C(O)—O—C(O)—) is linked via its two carbon atoms to two ortho carbons of the phenyl ring. Preferably, a is 0. In another embodiment, a is 0 and n is preferably 1 or 2.
- Further in structure I, R1, R2, R3, and R4 are each independently hydrogen, hydroxy, C1-C12 alkyl, C1-C12 perhaloalkyl, C1-C12 alkoxy, C1-C12 perhaloalkoxy, C2-C12 alkenyl, C2-C12 alkynyl, (C1-C6 alkyl)-O-(C1-C6 alkylene), or hydroxy(C1-C6 alkylene), wherein x and y are each independently an integer from 1 to 10. In one embodiment, R1, R2, R3, and R4 are each independently hydrogen, hydroxy, or C1-C12 alkyl, and x and y is each independently an integer from 1 to 6. More preferably R1, R2, R3, and R4 is each independently hydrogen or C1-C6 alkyl.
- R5 in structure I is a hydrogen or methyl group, and is preferably a methyl group.
- M in structure I is a carbonyl-containing group, in particular
wherein G and J are each independently oxygen or NR6, wherein R6 is hydrogen or C1-C6 alkyl; and m is 1, 2, 3, or 4. Preferably, M is
wherein G is oxygen, and m is 1, 2, or 3. When a is 1, n+m+q is 1, 2, 3, or 4, and when a is 0, n+m+is 1, 2, 3, 4, 5, or 6. - W in structure I is a hydrocarbyl linking group having a valency corresponding to z, the number of (meth)acrylate groups, plus one. W may be aromatic or aliphatic. Suitable aromatic groups are phenyl and napthyl, and suitable aliphatic groups are C1-C12 alkyl, cycloalkyl, alkenyl, or alkynyl groups.
-
- In structure III, n, q, M, A, and a are as described above. Preferably, a is 0 and n is 0 or 1.
- Further in structure I, R1, R2, R3, R4, R5, x, and y are as described above. R6 and R7 are each independently hydrogen, hydroxy, C1-C12 alkyl, C1-C12 perhaloalkyl, C1-C12 alkoxy, C1-C12 perhaloalkoxy, C2-C12 alkenyl, C2-C12 alkynyl, (C1-C6 alkyl)-O-(C1-C6 alkylene), or hydroxy(C1-C6 alkylene), wherein z is an integer of 1 to 5, preferably 1 to 3. In one embodiment, R1, R2, R3, R4, R6, and R7 are each independently hydrogen, hydroxy, or C1-C12 alkyl, and x and y is each independently an integer from 1 to 6. More preferably R1, R2, R3, R4, R6, and R7 is each independently hydrogen or C1-C6 alkyl.
- The polymerizable (meth)acrylate (I) may be synthesized, for example, from the reaction of a hydroxy-containing (meth)acrylate monomer and an aromatic compound comprising anhydride or carboxylic acid functionality or their synthetic equivalents (e.g., a carboxylic acid halide, for example chloride). An exemplary synthetic preparation includes the reaction of one mole of an aromatic anhydride, for example benzenetetracarboxylic acid dianhydride (BTAD) or pyromellitic dianhydride (PMDA), with two moles of a hydroxy-containing (meth)acrylate, for example caprolactone 2-(methacryloyloxy)ethyl ester (CLMA, or 2-(6-hydroxy-1-oxo-hexyloxy)ethyl methacrylate), at elevated temperature in the presence of a catalyst, for example a catalytic amount of stannous ethylhexanoate (SEH). The resulting reaction product contains two (meth)acrylate groups and two carboxylic acid groups. Any number of the remaining carboxylic acid groups may further be reacted with an additional hydroxy-containing (meth)acrylate monomer to form a modified polymerizable (meth)acrylate. The ratio of moles of hydroxy-containing (meth)acrylate monomer to moles of anhydride or carboxylic acid, as well as the reaction conditions and/or starting materials, may be varied to provide a wide range of polymerizable (meth)acrylate products.
- Exemplary aromatic compounds comprising anhydride functionality, carboxylic acid functionality, or a combination thereof useful to prepare the polymerizable (meth)acrylate of structure I include BTAD, PMDA, all isomers of benzenetetracarboxylic acid, preferably benzene-1,2,4,5-tetracarboxylic acid, 1,3-dihydro-1,3-dioxoisobenzofuran-4,5-dicarboxylic acid, 1,3-dihydro-1,3-dioxoisobenzofuran-5,6-dicarboxylic acid, trimellitic anhydride, trimellitic acid, terephthalic acid, phthalic acid, phthalic anhydride, benzoic acid, 4′-(4,4′-isopropylidenediphenoxy)-bis(phthalic anhydride) (IBA), and the like. Preferred aromatic anhydride and/or carboxylic acid compounds include BTAD, 1,3-dihydro-1,3-dioxoisobenzofuran-4,5-dicarboxylic acid, PMDA, benzene-1,2,4,5-tetracarboxylic acid, 1,3-dihydro-1,3-dioxoisobenzofuran-5,6-dicarboxylic acid, trimellitic anhydride, and trimellitic acid.
-
- A preferred hydroxy-containing (meth)acrylate monomer is a compound according to structure II wherein R1, R2, R3, and R4 are each hydrogen; x and y are each independently an integer from 1 to 5; M is
wherein G is oxygen; and R5 is hydrogen or methyl, more preferably methyl. Non-limiting examples of suitable hydroxy-containing (meth)acrylate monomers according to structure II include CLMA, caprolactone 2-(acryloyloxy) ethyl ester, and 3-hydroxy-1-oxopropyl (meth)acrylate. The most preferred hydroxy-containing (meth)acrylate monomers are CLMA and caprolactone 2-(acryloyloxy)ethyl ester. Mixtures of two or more different hydroxy-containing (meth)acrylates of formula II may also be used. - Methods of synthesizing the hydroxy-containing (meth)acrylate monomers according to structure II can be found in the art. For example, CLMA may be prepared by the condensation of ε-caprolactone and 2-hydroxyethyl methacrylate. In yet another exemplary synthetic scheme, isocyanate alkyl (meth)acrylate (e.g., isocyanate methyl (meth)acrylate) may be reacted with a suitably monoprotected amino alcohol or dialcohol followed by deprotection to result in a hydroxy-containing methacrylate comprising urea or carbamate functionality.
- When the polymerizable (meth)acrylate is prepared by the reaction of a hydroxy-containing (meth)acrylate monomer with an aromatic anhydride and/or carboxylic acid, the ratio of moles of hydroxy-containing (meth)acrylate monomer to the moles of aromatic anhydride, carboxylic acid, or its equivalent may be selected to obtain a resin that provides desired properties of adhesion and reduced shrinkage upon polymerization. The ratio of moles of hydroxy-containing (meth)acrylate monomer to moles of aromatic anhydride and/or carboxylic acid may be about 0.1 to about 5, preferably about 0.5 to about 4, more preferably about 0.75 to about 3, and yet more preferably about 1 to about 2.
- The catalyst used to prepare the polymerizable (meth)acrylate according to the general structure (I) may be selected from metal organic catalysts comprising tin or titanium. Suitable non-limiting examples of tin-containing catalysts are dibutyltin dilaurate, dibutyltin maleate, dibutyltin diacetate, dioctyltin maleate, dibutyltin phthalate, stannous octoate, stannous naphthenate, stannous stearate, stannous 2-ethyl hexanoate, dibutyltin diacetylacetonate, dibutyltin oxide, and combinations comprising at least one of the foregoing tin based catalysts. Suitable non-limiting examples of titanium-based catalysts are tetrabutyl titanate, tetrapropyl titanate, tetraisopropyl titanate, triethanolamine titanate, titanium tetraacetylacetonate, and combinations comprising at least one of the foregoing titanium based catalysts. The preferred catalysts are stannous octoate or stannous 2-ethyl hexanoate.
- It is generally desirable to use the catalyst in an amount of about 0.10 to about 10 mole percent based on the total moles of the reactant mixture. Within this range it is generally desirable to utilize the catalyst in an amount about 1 to about 8, preferably about 2 to about 7, and most preferably about 3 to about 6 mole percent based on the total moles of the reactants.
- In another embodiment, the polymerizable (meth)acrylate of structure (I) may be formed by reaction of an aromatic compound comprising anhydride functionality, carboxylic acid functionality, or a combination thereof with a mixture comprising a hydroxy-containing (meth)acrylate of formula II and an additional, different hydroxy-containing methacrylate of formula IV:
wherein W and R5 are as defined above. Exemplary suitable hydroxy-containing (meth)acrylate monomers of this type include compounds comprising two or more (meth)acrylate groups, for example, glyceryl di(meth)acrylate, glycerol di(meth)acrylate, trimethylolpropane di(meth)acrylate; pentaerythritol tri(meth)acrylate and the like. Preferably, the different hydroxy-containing (meth)acrylate is of structure V:
wherein R6 and R7 are each independently hydrogen, hydroxy, C1-C12 alkyl, C1-C12 perhaloalkyl, C1-C12 alkoxy, C1-C12 perhaloalkoxy, C2-C12 alkenyl, C2-C12 alkynyl, (C1-C6 alkyl)-O-(C1-C6 alkylene), or hydroxy(C1-C6 alkylene); z is an integer from 1 to 10; and R5 is hydrogen or methyl. In a preferred embodiment, the additional hydroxy (meth)acrylate according to structure V comprises a compound wherein R6 and R7 are each independently hydrogen, C1-C12 alkyl, or hydroxy; and z is an integer from 1 to 10; and R5 is methyl. Exemplary compounds include 2-hydroxyethyl methyacrylate (HEMA), 2-hydroxyethyl acrylate, hydroxypropyl (meth)acrylate, and glyceryl mono(meth)acrylate. Mixtures of the additional monomers may also be used. - When the polymerizable (meth)acrylate of structure I comprising free anhydride and/or carboxylic acid groups is reacted with an additional hydroxy-containing (meth)acrylate monomer, the ratio of the moles of additional hydroxy-containing (meth)acrylate monomer to moles of anhydride and/or carboxylic acid of structure I, monomer II, and the additional monomer(s) may be selected to provide a modified polymerizable (meth)acrylate possessing desired properties. Generally the ratio of moles of additional hydroxy-containing (meth)acrylate monomer to moles of anhydride and/or carboxylic acid groups of structure (I) may be about 0.1:1 to about 5:1, preferably about 0.5:1 to about 4:1, more preferably about 0.75:1 to about 3:1, and yet more preferably about 1:1 to about 2:1.
- An exemplary polymerizable (meth)acrylate in accordance with the present invention is the reaction product of BTAD with CLMA, having structures VIa and/or VIb as follows:
Another exemplary polymerizable (meth)acrylate in accordance with the present invention is the reaction product of BTAD with mixtures of CLMA and HEMA, having the structure (VIIa) and/or (VIIb) as follows: - The polymerizable (meth)acrylates may be used alone or in combination with other co-polymerizable, ethylenically unsaturated monomers and/or oligomers. For example, one or more other co-polymerizable, ethylenically unsaturated monomers and/oligomers containing carboxylic acid(s), phosphoric acid(s), sulfonic acid(s) or their anhydride(s) may be utilized in combination with the polymerizable (meth)acrylates of this invention. Mixtures comprising the polymerizable (meth)acrylate and other components such as polymerization initiators, additives, and fillers may be prepared to form dental materials suitable for use as dental adhesives, dental cements, dental filling materials, root canal sealing/filling materials, and/or other dental restorative materials such as crown and bridge materials, provisional crown and bridge materials, and the like. It is generally desirable to use the polymerizable (meth)acrylate in an amount of about 1 to about 99 weight percent based on the total weight of the dental restorative material. Within this range it is generally desirable to use the polymerizable (meth)acrylate in an amount of about 10 to about 95 weight percent, preferably about 30 to about 90 weight percent, and most preferably about 50 to about 80 weight percent based on the total weight of the dental restorative material.
- Known viscous resins may be used in combination with the polymerizable (meth)acrylate to provide a dental restorative material. Non-limiting examples include polyurethane dimethacrylates (PUDMA), diurethane dimethacrylates (DUDMA), and/or the polycarbonate dimethacrylate (PCDMA) disclosed in U.S. Pat. Nos. 5,276,068 and 5,444,104 to Waknine, which is the condensation product of two parts of a hydroxyalkylmethacrylate and 1 part of a bis(chloroformate). Another advantageous resin having lower water sorption characteristics is an ethoxylated bisphenol A dimethacrylate (EBPDMA) as disclosed in U.S. Pat. No. 6,013,694 to Jia, et al. Still another useful resin material is disclosed in U.S. Pat. No. 6,787,629 to Jia, et al. An especially useful methacrylate resin is BisGMA.
- Diluent monomers may be used to increase the surface wettability of the composition and/or to decrease the viscosity of the polymerization medium. Suitable diluent monomers include those known in the art such as hydroxyalkyl (meth)acrylates, for example 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate; ethylene glycol (meth)acrylates, including ethylene glycol methacrylate, diethylene glycol methacrylate, tri(ethylene glycol) dimethacrylate and tetra(ethylene glycol) dimethacrylate; and diol dimethacrylates such as 1,4-butanediol di(meth)acrylate, dodecane diol di(meth)acrylate, or 1,6-hexanediol di(meth)acrylate, particularly 1,6-hexanediol dimethacrylate (HDDMA). Other suitable monomers include polyethylene glycol mono(meth)acrylate; glycerol di(meth)acrylate; trimethylolpropane di(meth)acrylate; pentaerythritol tri(meth)acrylate; the (meth)acrylate of phenyl glycidyl ether; and the like. Tri(ethylene glycol) dimethacrylate (TEGDMA) is particularly preferred.
- Diluent monomers or viscous resins, when present, are incorporated into the dental restorative materials in an amount of about 1 to about 70 weight percent of the total dental restorative material.
- The optional filler system may comprise one or more of the inorganic fillers currently used in dental composite materials. Preferred fillers include those, which are capable of being covalently bonded to the polymerizable (meth)acrylate matrix itself or to a coupling agent (e.g., silanes) that is covalently bonded to both. Examples of suitable filling materials include but are not limited to, silica, quartz, strontium silicate, strontium borosilicate, lithium silicate, lithium alumina silicate, amorphous silica, ammoniated or deammoniated calcium phosphate, tricalcium phosphate alumina, zirconia, tin oxide, titania and combinations comprising at least one of the foregoing fillers. Some of the aforementioned inorganic filling materials and methods of preparation thereof are known in the art, as disclosed in U.S. Pat. No. 4,544,359 and No. 4,547,531 to Waknine, pertinent portions of which are incorporated herein by reference. Organic-inorganic fillers of POSS™ (Hybrid Plastics) can be incorporated into the composites as disclosed in U.S. Patent Application Publication 2002/0198282 A1. Other organic-inorganic fillers such as zirconium methacrylate and zirconium dimethacrylate under the codes of CXZR050 and CXZR051 (Gelest, Inc.) can also be used. Suitable high refractive index filler materials such as high refractive index silica glass fillers; calcium silicate based fillers such as apatites, hydroxyapatites or modified hydroxyapatite compositions may also be used. Alternatively, inert, non-toxic radiopaque materials such as bismuth oxide (Bi2O3), bismuth oxychloride, zirconium oxide, barium sulfate, and bismuth subcarbonate in micro- or nano scaled sizes may be used. In addition, fibrous fillers such as those disclosed in U.S. Pat. Nos. 6,013,694, 6,403,676 and 6,270,562 to Jia and Jia et al. may also be used.
- Suitable fillers have particle sizes of about 0.01 to about 5.0 micrometers, and may further comprise bound or unbound silicate colloids of about 0.001 to about 0.2 micrometers. These additional fillers may also be treated with a silane-coupling agent to increase adhesion with the polymerizable, (meth)acrylate. Commercially available silane treated fumed silica based on Aerosil A200 can be obtained from Degussa Corp under the names of Aerosil R711 and R7200.
- The amount of total filler system in the dental restorative material can vary from about 1 to about 90 weight percent based on the total weight of the dental restorative material. The amount used is determined by the requirements of the particular application. Thus, for example, crown and bridge materials generally comprise about 60 to about 90 weight percent filler; luting cements comprise about 20 to about 80 weight percent filler; sealants generally comprise about 1 to about 20 weight percent filler; adhesives generally comprise about 1 to about 30 weight percent filler; and restorative materials comprise about 50 to about 90 weight percent filler, with the remainder in all cases being the polymerizable (meth)acrylate and other optionally added resins.
- The polymerizable (meth)acrylate may be used together with a curing system, which generally includes polymerization initiators; polymerization accelerators; ultraviolet light absorbers; antioxidants; and other additives known in the art.
- Suitable polymerization initiators are those initiators that can be utilized in UV-activated cure or visible light-activated cure compositions. For example, visible light-curable compositions employ light-sensitive compounds, including but not being limited to benzil, benzoin, benzoin methyl ether, DL-camphorquinone (CQ), and benzil diketones. Either UV-activated cure or visible light-activated cure (approximately 230 to 750 nanometer) is acceptable. The amount of photoinitiator is selected according to the curing rate desired. A minimal catalytically effective amount is generally about 0.01 weight percent of the total dental resin composition, and will lead to a slower cure. Faster rates of cure are achieved with amounts of catalyst in the range from greater than about 0.01 percent to about 5 weight percent of the total dental resin composition. The total dental resin composition is the total weight of the polymerizable (meth)acrylate and other resinous materials, such as for example, resinous diluents, which are used in the dental restorative material.
- Alternatively, the dental restorative material may be formulated as a self-curing system. Self-curing dental composite materials will generally contain free radical polymerization initiators such as, for example, a peroxide in an amount of about 0.01 to about 1.0 weight percent of the total resin dental composite material. Particularly suitable free radical initiators are lauryl peroxide, tributyl hydroperoxide and, more particularly benzoyl peroxide (BPO).
- Polymerization accelerators suitable for use are the various organic tertiary amines well known in the art. In visible light-curable dental restorative materials, the tertiary amines are generally (meth)acrylate derivatives such as dimethylaminoethyl methacrylate and, particularly, diethylaminoethyl methacrylate (DEAEMA) in an amount of about 0.05 to about 0.5 weight percent of the total dental restorative material. In the self-curing dental composite materials, the tertiary amines are generally aromatic tertiary amines, preferably tertiary aromatic amines such as ethyl 4-(dimethylamino)benzoate (EDMAB), 2-[4-(dimethylamino)phenyl]ethanol, N,N-dimethyl-p-toluidine (DMPT), and bis(hydroxyethyl)-p-toluidine (DHEPT). Such accelerators are generally present in an amount of about 0.5 to about 4.0 weight percent of the total dental restorative material.
- It is furthermore preferred to employ an ultraviolet absorber in an amount of about 0.05 to about 5.0 weight percent of the total dental restorative material. Such UV absorbers are particularly desirable in the visible light-curable dental restorative materials in order to avoid discoloration of the resin from incident ultraviolet light. Suitable UV absorbers are the various benzophenones, particularly UV-5411 available from American Cyanamid Company.
- In one embodiment, the polymerizable (meth)acrylate is prepared by reacting an aromatic compound comprising anhydride and/or carboxylic acid functionality with a hydroxy-containing (meth)acrylate monomer in the presence of a catalyst. The resulting polymerizable (meth)acrylate is then formulated into a dental restorative material by mixing with the filler system and the curing system. The dental restorative material is then applied to the tooth to be repaired, and cured.
- Alternatively, the dental restorative material may be formulated as a two-part system, wherein the first part can comprise the polymerizable (meth)acrylate and the filler system. The second part can comprise the curing system and optional diluent monomers. When necessary, the two parts are metered out and then mixed using a spatula. The cure may be initiated through the use of UV light or by raising the temperature of the mixture. The dental restorative material thus obtained is then placed in the tooth to be restored after the tooth is appropriately prepared. Methods for use of the above-described compositions are well known in the art.
- As used herein, the term “(meth)acrylate” is intended to encompass both acrylate and methacrylate groups. All ranges disclosed herein are inclusive and combinable. In addition, all patents are incorporated by reference in their entirety.
- The invention is further illustrated by the following non-limiting examples.
- In a reaction flask, 1 mole (218 g) of 1,2,4,5-benzenetetracarboxylic dianhydride (BTAD) and 2.05 mole (500 g) of 2-(caprolactone)ethyl methacrylate (CLMA) were mixed and heated in an oil bath while mixing until the mixture becomes liquid. A catalytic amount of tin(II) 2-ethylhexanoate (SEH) was added into the flask slowly and the reaction monitored by Fourier transform infrared spectroscopy (FTIR). The reaction was stopped when the anhydride peak at 1782 cm−1 disappeared. The final product BTAD-CLMA is a viscous liquid.
- In a reaction flask, 1 mole (218 g) of 1,2,4,5-benzenetetracarboxylic dianhydride (BTAD), 1.05 mol (500 g) of 2-(caprolactone)ethyl methacrylate (CLMA) and 1 mol (130 g) 2-hydroxyethyl methacrylate (HEMA) was mixed. The mixture was heated in an oil bath while mixing until the mixture became liquid. A catalytic amount of tin(II) 2-ethylhexanoate (SEH) was added into the flask slowly and the reaction monitored by FTIR and stopped when the anhydride peak at 1782 cm−1 disappeared. The final product BTAD-CLMA-HEMA is a viscous liquid.
- The synthesized resins BTAD-CLMA and BTAD-CLMA-HEMA were each mixed with a conventional resin and diluent (PUDMA and HDDMA)in a weight ratio of 50/40/10. Quantities of 0.2 wt % CQ and 0.4 wt % EDMAB were added as photoinitiators. The samples were cured for a total four minutes using visible light with CureLite™ Plus curing box (Pentron Corp.) Samples were then trimmed and stored in water at 37° C. for 24 hours before testing.
- Three point bending strength or flexural strength (MOR) was measured on all samples using an ATS machine as described in ISO 4049 for Resin Based Filling Materials (1997). Results are shown in Table 1, wherein standard deviations are in parentheses.
TABLE 1 BTAD-CLMA/ BTAD-CLMA-HEMA/ UDMA/HDDMA UDMA/HDDMA (Resin 1) (Resin 2) MOR 97(8) 83(10) Mpa (σ) -
Resin 1 andResin 2 were further used to make a light-curable dental composite with the addition of treated silica filler (R7200 from Degussa), a sol-gel processed zirconium silicate filler as disclosed in U.S. Patent Publ. No. 2003/0125444 A1 and Schott glass filler (Schott 8235, available from Schott Electronic Packaging Gmbh, Germany). The same filler combination and loading (78 wt. % filler) were used in to formComposite 1 fromResin 1 andComposite 2 fromResin 2. The composites were tested and the MOR results are shown in Table 2.TABLE 2 Composite 1 Composite 2MOR 149(12) 124(17) Mpa (σ) - Samples of self-curing compositions with and without BTAD-CLMA in the catalyst part were prepared to evaluate the effect BTAD-CLMA on cure. The samples, designated SC1 and SC2, were each formed from two paste components, a catalyst paste and a base paste. The catalyst past and base paste were each prepared from a resin and a filler that have the compositions shown in Table 3. The SC1 catalyst resin contains 10 wt. % of BTAD-CLMA, while SC2 does not. Other components for samples SC1 and SC2 are similar. In each sample,
Catalyst paste 1 andCatalyst paste 2, respectively, were mixed in 1:1 wt. ratio with the base paste.TABLE 3 SC1 SC2 (Control) Resin Catalyst resin 1: Catalyst resin 2: compo- BPO 3 wt %, BHT 0.1BPO 3 wt %, BHT 0.1sitions wt % in BisGMA/HDDMA/ wt % in BisGMA/HDDMA used to BTADCLMA (wt. Ratio: (wt. Ratio: 70/30) form 60/30/10) Base resin: catalyst Base resin: DHEPT 1.5 wt %, BHT and base DHEPT 1.5 wt %, BHT 0.05 wt % in EBPADMA pastes 0.05 wt % in EBPADMA Paste Catalyst paste 1: Catalyst paste 2: Compo- Catalyst resin 1: 35 Catalyst resin 2: 35 nents wt % wt % Filler: 65 wt % of Filler: 65 wt % of treated silica and treated silica and glass filler glass filler Base paste: Base paste: Base resin: 30 wt % Base resin: 30 wt % Filler: 70 wt % of Filler: 70 wt % of treated silica and treated silica and glass filler, barium glass filler, barium sulfate and calcium sulfate and calcium hydroxide hydroxide - Both samples were allowed to age, and portions of the samples were taken periodically to determine the gel times and setting times. The FIGURE shows the stability test results of samples SC1 and SC2 at room temperature for 8 weeks. Sample SC1 shows stable gel time and setting time during the 8 weeks storage at room temperature, but sample SC2 shows increasing gel time and setting time.
- The present polymerizable (meth)acrylates resins can be used to prepare a light curable, one-component adhesive composite for tooth restorations, wherein the composites can be used without a separate dental bonding procedure prior to a the application of the material. Such procedures can be time-consuming, and their elimination is highly advantageous. An exemplary composition is illustrated in the table below:
Parts per Components Function in the composition hundred BTAD-CLMA-HEMA Resin matrix component and 20 adhesion promoter HEMA A co-polymerizable resin 20 diluent and hydrophilicity modifier for the composition Camphorquinone Photo-initiator 0.1 Lucirin-TPO Co-photo-initiator 0.2 BHT stabilizer 0.01 Silane treated barium glass filler 55 (Schott 8235) Amorphous silica Filler and rheology/viscosity 4.69 (Degussa R 7200) modifier - The above composition has a flowable consistency, which allows delivery of the composite through a cannula, for example a needle tip directly onto a tooth surface. Again, it has been found that a separate bonding procedure, i.e. an additional bonding adhesive is not necessary. These compositions may be used, for example, for cementing a veneer, lining a tooth cavity underneath a regular dental restorative composite, sealing a root canal coronal end, placing as a direct tooth filling, securing an orthodontic bracket, or the like.
- The present polymerizable (meth)acrylates resins can be used to prepare self and/or dual-curable two-component composites suitable for use as an adhesive luting cement, a core build-up material, a root canal filling/sealing material, or the like. In an advantageous feature, use of a separate bonding procedure before using the composite material is not necessary. An exemplary composition is illustrated in the table below.
Base Catalyst Components Paste Paste BTAD-CLMA 15 4-methacryloxyethyl trimellitic anhydride 15 HEMA 5 20 UDMA 35 BisGMA 10 BHT 0.01 0.1 EDMAB 0.5 Camphorquinone 0.2 DHEPT 1.0 BPO 2.0 Silane treated barium glass filler (Schott 8235) 30 5 Al—Ca—F-silicate filler 15 BiOCl 35 Amorphous silica (OX-50) 3.29 7.9 - In self-cure mode, the working time and setting time of the above composition is about three minutes and four and half minutes, respectively, when the base and catalyst is mixed in 1:1 ratio by volume and the material is not subject to a second curing process. In dual-cure mode, when the material, upon mixing the base and catalyst, is subject to a dental visible light-curing source, the mass of the material will harden immediately upon the photoinitiation.
- The Table below shows the results of cementation/bonding tests of the present polymerizable (meth)acrylates resin composite compositions between dentin and a ceramic (3G™ ceramic material, Pentron Corp., Wallingford, Conn.). The bonding test method was as follows:
- 1. 3G™ ceramic rods were fabricated with a dental porcelain furnace according to the ceramic firing temperature and conditions of the product. The 3G™ ceramic rods used for the bonding test have final dimensions of about 3.2 mm diameter and 6-8 mm length, on which one end of the rod was sandblasted, cleaned and then silane treated as per the product instructions. The treated end will be contacting the bonding cement as in a tooth restoration. Each test group contains 5 samples.
- 2. Teeth samples were prepared to expose the dentin and then the teeth were mounted with an acrylic material leaving the dentin exposed, which were then subject to sand paper grinding under wet condition to have a same surface pattern for all the test groups.
- 3. The cement materials were mixed according to the product instructions and applied onto the prepared, briefly dried tooth surface. The ceramic rod was then seated onto the cement surface under a 500 gram load with the aid of a BenCor Multi-test device (Danville Engineering, CA).
- 4. After the cement hardened, the bonded samples were transferred into a 100% humidity chamber held at 37° C. for 24 hours before the debond test.
- 5. The debond test was done in push shear mode using a BenCor testing device on an ATS testing machine. The load at which the bonded ceramic rod broke was recorded and the shear bonding strength of the testing sample was then calculated based on the rod surface area. Standard deviation is reported in parentheses.
Shear Bonding Strength (the stress needed to break the bond between the 3G ceramic and the tooth Cement Materials surface), MPa (S.D.) Notes Cement material 12.2 (2.8) A paste-paste self- as in Example 6 adhesive resin cement Fleck's ® Zinc 0.5 (0.8) A powder-liquid Cement (A con- cement system as a ventional zinc control available phosphate cement from Mizzy, Inc., for dental Cherry Hill, NJ. restorations) Lute-It! ™ resin 0.3 (1.2) A paste-paste conven- cement, shade A2 tional methacrylate resin cement as a control and used without a separated bonding procedure before the applica- tion of the cement available from Pen- tron Corp., Walling- ford, CT. Lute-It ™ resin 14.8 (1.6) Before apply the cement, shade A2, mixed cement onto used in conjunc- the tooth surface, a tion with Bond-1 ™ separated bonding dental adhesive procedure is per- formed per the in- struction of the Bond-1 ™ dental bonding system, available from Pentron Corp., Wallingford, CT. - While the invention has been described with reference to exemplary embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from the essential scope thereof. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed as the best mode contemplated for carrying out this invention, but that the invention will include all embodiments falling within the scope of the appended embodiments.
Claims (15)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US11/046,093 US7700667B2 (en) | 2004-01-29 | 2005-01-28 | Dental resin composition, method of manufacture, and method of use thereof |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US54014804P | 2004-01-29 | 2004-01-29 | |
US11/046,093 US7700667B2 (en) | 2004-01-29 | 2005-01-28 | Dental resin composition, method of manufacture, and method of use thereof |
Publications (2)
Publication Number | Publication Date |
---|---|
US20050192374A1 true US20050192374A1 (en) | 2005-09-01 |
US7700667B2 US7700667B2 (en) | 2010-04-20 |
Family
ID=34889741
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US11/046,093 Active 2027-06-05 US7700667B2 (en) | 2004-01-29 | 2005-01-28 | Dental resin composition, method of manufacture, and method of use thereof |
Country Status (1)
Country | Link |
---|---|
US (1) | US7700667B2 (en) |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20060270752A1 (en) * | 2005-05-26 | 2006-11-30 | Ada Foundation | Dental releasing materials |
US20070049656A1 (en) * | 2005-09-01 | 2007-03-01 | Pentron Clinical Technologies, Inc | Dental resin composition, method of manufacture, and method of use thereof |
US20070197682A1 (en) * | 2006-02-23 | 2007-08-23 | Weitao Jia | Self etch all purpose dental cement composition, method of manufacture, and method of use thereof |
US20080242761A1 (en) * | 2006-02-23 | 2008-10-02 | Weitao Jia | Self etch all purpose dental compositions, method of manufacture, and method of use thereof |
US20080286724A1 (en) * | 2007-05-18 | 2008-11-20 | Ormco Corporation | Orthodontic adhesives |
EP2230286A1 (en) * | 2009-03-20 | 2010-09-22 | Pentron Clinical Technologies, LLC | Dental resin composition, method of manufacture, and method uf use thereof |
US20110171608A1 (en) * | 2006-02-23 | 2011-07-14 | Pentron Clinical Technologies, L.L.C. | Self etch all purpose dental cement composition and method of use thereof |
US8053490B2 (en) | 2009-05-18 | 2011-11-08 | Pentron Clinical Technologies, Llc | Pre-treated acid-reactive fillers and their use in dental applications |
US20160045403A1 (en) * | 2013-03-15 | 2016-02-18 | The Regents Of The University Of California | Calcium sulfate-resin hybrid materials and methods of using and making the same |
Citations (49)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3066112A (en) * | 1959-01-30 | 1962-11-27 | Rafael L Bowen | Dental filling material comprising vinyl silane treated fused silica and a binder consisting of the reaction product of bis phenol and glycidyl acrylate |
US3194784A (en) * | 1959-01-30 | 1965-07-13 | Rafael L Bowen | Silica-resin direct filling material and method of preparation |
US3926906A (en) * | 1968-06-14 | 1975-12-16 | Johnson & Johnson | Dental filling package |
US4148988A (en) * | 1977-06-28 | 1979-04-10 | Mitsui Petrochemical Industries Ltd. | Curable composition |
US4504635A (en) * | 1982-11-02 | 1985-03-12 | Union Carbide Corporation | Process for the preparation of polymeric compositions |
US4544359A (en) * | 1984-01-13 | 1985-10-01 | Pentron Corporation | Dental restorative material |
US4547531A (en) * | 1984-08-02 | 1985-10-15 | Pentron Corporation | Two component (paste-paste) self-curing dental restorative material |
US4659751A (en) * | 1983-01-10 | 1987-04-21 | American Dental Association Health Foundation | Simplified method for obtained strong adhesive bonding of composites to dentin, enamel and other substrates |
US4691045A (en) * | 1984-12-06 | 1987-09-01 | Nippon Shokubai Kagaku Co., Ltd. | Hydroxyl group-containing (meth)acrylate oligomer, prepolymer therefrom, and method for use thereof |
US4732943A (en) * | 1985-04-24 | 1988-03-22 | Commonwealth Scientific And Industrial Research Organization | Dental restorative material |
US4786749A (en) * | 1986-02-20 | 1988-11-22 | Union Carbide Corporation | Carboxyl-terminated lactone acrylates |
US4883899A (en) * | 1986-01-08 | 1989-11-28 | Nippon Paint Co., Ltd. | End carboxyl bearing reactive vinyl monomers and preparation thereof |
US5171763A (en) * | 1990-12-14 | 1992-12-15 | Tokuyama Soda Kabushiki Kaisha | Curable composition |
US5260476A (en) * | 1990-12-14 | 1993-11-09 | Tokuyama Soda Kabushiki Kaisha | Diacrylate compounds |
US5264513A (en) * | 1990-02-15 | 1993-11-23 | Kabushiki Kaisha Shofu | Primer composition |
US5276068A (en) * | 1985-03-29 | 1994-01-04 | Jeneric/Pentron, Inc. | Dental resin materials |
US5348988A (en) * | 1990-04-12 | 1994-09-20 | Bisco, Inc. | Dentin bonding system |
US5525648A (en) * | 1991-12-31 | 1996-06-11 | Minnesota Mining And Manufacturing Company | Method for adhering to hard tissue |
US5756560A (en) * | 1994-02-01 | 1998-05-26 | The United States Of America As Represented By The Secretary Of The Commerce | Method and composition for promoting improved adhesion to substrates |
US5925690A (en) * | 1995-11-20 | 1999-07-20 | Tokuyama Corproation | Dental primer composition and kit |
US5969000A (en) * | 1997-01-17 | 1999-10-19 | Jeneric Pentron Incorporated | Dental resin materials |
US6013694A (en) * | 1997-10-16 | 2000-01-11 | Jeneric/Pentron Incorporated | Dental composites comprising ground, densified, embrittled glass fiber filler |
US6071983A (en) * | 1993-08-02 | 2000-06-06 | Sun Medical Co., Ltd. | Primer composition and curable composition |
US6147137A (en) * | 1998-09-10 | 2000-11-14 | Jeneric/Pentron Incorporated | Dental primer and adhesive |
US6217644B1 (en) * | 1998-08-09 | 2001-04-17 | Gc Corporation | Dental adhesive set |
US6291548B1 (en) * | 1998-08-11 | 2001-09-18 | Gc Corporation | Dental cement composition |
US6326417B1 (en) * | 1999-10-21 | 2001-12-04 | Jeneric/Pentron Incorporated | Anti-microbial dental compositions and method |
US20020045678A1 (en) * | 2000-08-22 | 2002-04-18 | Lopez Larry A. | Dental restorative compositions and method of use thereof |
US20020082317A1 (en) * | 1998-09-11 | 2002-06-27 | Sultan Chemists, Inc. | Dental adhesive compositions with desensitizing agents |
US20020120033A1 (en) * | 2000-08-11 | 2002-08-29 | Weitao Jia | Dental/medical compositions comprising degradable polymers and methods of manufacture thereof |
US20030055124A1 (en) * | 2001-08-10 | 2003-03-20 | Klee Joachim E. | Hydrolysis stable one-part self-etching, self-priming dental adhesive |
US20030125444A1 (en) * | 2001-11-02 | 2003-07-03 | Weitao Jia | Dental resin materials, method of manufacture, and uses thereof |
US20030175659A1 (en) * | 2002-02-07 | 2003-09-18 | Amer Tiba | Multifunctional dentin bonding agent |
US20030207960A1 (en) * | 2001-05-10 | 2003-11-06 | Weitao Jia | Self-etching primer adhesive and method of use therefor |
US6649669B2 (en) * | 2001-12-28 | 2003-11-18 | American Dental Association Health Foundation | Single solution bonding formulation |
US6653365B2 (en) * | 2001-05-01 | 2003-11-25 | Pentron Clinical Technologies, Llc | Dental composite materials and method of manufacture thereof |
US6759449B2 (en) * | 2000-11-28 | 2004-07-06 | Tokuyama Dental Corporation | Dental adhesive composition |
US20040156795A1 (en) * | 2001-07-09 | 2004-08-12 | Kimiya Nemoto | Dental self-etching primer |
US6815470B2 (en) * | 2000-09-26 | 2004-11-09 | Tokuyama Corporation | Dental catalyst for chemical polymerization and use thereof |
US20040229973A1 (en) * | 2003-05-13 | 2004-11-18 | Junjie Sang | Dental adhesive compositions and methods |
US20040235981A1 (en) * | 2003-05-19 | 2004-11-25 | Kerr Corporation | Two-part self-adhering dental compositions |
US20050014861A1 (en) * | 2003-07-17 | 2005-01-20 | Kerr Corporations | Methods of using two-part self-adhering dental compositions |
US20050020720A1 (en) * | 2003-07-02 | 2005-01-27 | Ada Foundation | Remineralizing dental cements |
US20050038135A1 (en) * | 2001-05-01 | 2005-02-17 | Shuhua Jin | Dental composite materials and method of manufacture thereof |
US20050049326A1 (en) * | 2003-08-29 | 2005-03-03 | Park Kwang Soo | Dental self-curing resin cement compositions |
US6939900B2 (en) * | 1997-07-17 | 2005-09-06 | 3M Innovative Properties Company | Dental resin cements having improved handling properties |
US20050277706A1 (en) * | 2004-06-09 | 2005-12-15 | Han Dong K | Highly functional dental adhesive composition |
US20070197683A1 (en) * | 2006-02-23 | 2007-08-23 | Pentron Clinical Technologies, Inc | Self etch all purpose dental compositions, method of manufacture, and method of use thereof |
US20080242761A1 (en) * | 2006-02-23 | 2008-10-02 | Weitao Jia | Self etch all purpose dental compositions, method of manufacture, and method of use thereof |
-
2005
- 2005-01-28 US US11/046,093 patent/US7700667B2/en active Active
Patent Citations (53)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3194784A (en) * | 1959-01-30 | 1965-07-13 | Rafael L Bowen | Silica-resin direct filling material and method of preparation |
US3066112A (en) * | 1959-01-30 | 1962-11-27 | Rafael L Bowen | Dental filling material comprising vinyl silane treated fused silica and a binder consisting of the reaction product of bis phenol and glycidyl acrylate |
US3926906A (en) * | 1968-06-14 | 1975-12-16 | Johnson & Johnson | Dental filling package |
US4148988A (en) * | 1977-06-28 | 1979-04-10 | Mitsui Petrochemical Industries Ltd. | Curable composition |
US4504635A (en) * | 1982-11-02 | 1985-03-12 | Union Carbide Corporation | Process for the preparation of polymeric compositions |
US4659751A (en) * | 1983-01-10 | 1987-04-21 | American Dental Association Health Foundation | Simplified method for obtained strong adhesive bonding of composites to dentin, enamel and other substrates |
US4544359A (en) * | 1984-01-13 | 1985-10-01 | Pentron Corporation | Dental restorative material |
US4547531A (en) * | 1984-08-02 | 1985-10-15 | Pentron Corporation | Two component (paste-paste) self-curing dental restorative material |
US4691045A (en) * | 1984-12-06 | 1987-09-01 | Nippon Shokubai Kagaku Co., Ltd. | Hydroxyl group-containing (meth)acrylate oligomer, prepolymer therefrom, and method for use thereof |
US5276068A (en) * | 1985-03-29 | 1994-01-04 | Jeneric/Pentron, Inc. | Dental resin materials |
US4732943A (en) * | 1985-04-24 | 1988-03-22 | Commonwealth Scientific And Industrial Research Organization | Dental restorative material |
US4883899A (en) * | 1986-01-08 | 1989-11-28 | Nippon Paint Co., Ltd. | End carboxyl bearing reactive vinyl monomers and preparation thereof |
US4786749A (en) * | 1986-02-20 | 1988-11-22 | Union Carbide Corporation | Carboxyl-terminated lactone acrylates |
US5264513A (en) * | 1990-02-15 | 1993-11-23 | Kabushiki Kaisha Shofu | Primer composition |
US5348988A (en) * | 1990-04-12 | 1994-09-20 | Bisco, Inc. | Dentin bonding system |
US5260476A (en) * | 1990-12-14 | 1993-11-09 | Tokuyama Soda Kabushiki Kaisha | Diacrylate compounds |
US5171763A (en) * | 1990-12-14 | 1992-12-15 | Tokuyama Soda Kabushiki Kaisha | Curable composition |
US5525648A (en) * | 1991-12-31 | 1996-06-11 | Minnesota Mining And Manufacturing Company | Method for adhering to hard tissue |
US6071983A (en) * | 1993-08-02 | 2000-06-06 | Sun Medical Co., Ltd. | Primer composition and curable composition |
US5756560A (en) * | 1994-02-01 | 1998-05-26 | The United States Of America As Represented By The Secretary Of The Commerce | Method and composition for promoting improved adhesion to substrates |
US5925690A (en) * | 1995-11-20 | 1999-07-20 | Tokuyama Corproation | Dental primer composition and kit |
US5969000A (en) * | 1997-01-17 | 1999-10-19 | Jeneric Pentron Incorporated | Dental resin materials |
US6939900B2 (en) * | 1997-07-17 | 2005-09-06 | 3M Innovative Properties Company | Dental resin cements having improved handling properties |
US6013694A (en) * | 1997-10-16 | 2000-01-11 | Jeneric/Pentron Incorporated | Dental composites comprising ground, densified, embrittled glass fiber filler |
US6217644B1 (en) * | 1998-08-09 | 2001-04-17 | Gc Corporation | Dental adhesive set |
US6291548B1 (en) * | 1998-08-11 | 2001-09-18 | Gc Corporation | Dental cement composition |
US6147137A (en) * | 1998-09-10 | 2000-11-14 | Jeneric/Pentron Incorporated | Dental primer and adhesive |
US20040054027A1 (en) * | 1998-09-11 | 2004-03-18 | Sultan Chemists, Inc. | Dental adhesive compositions with desensitizing agents |
US20020082317A1 (en) * | 1998-09-11 | 2002-06-27 | Sultan Chemists, Inc. | Dental adhesive compositions with desensitizing agents |
US6326417B1 (en) * | 1999-10-21 | 2001-12-04 | Jeneric/Pentron Incorporated | Anti-microbial dental compositions and method |
US20020120033A1 (en) * | 2000-08-11 | 2002-08-29 | Weitao Jia | Dental/medical compositions comprising degradable polymers and methods of manufacture thereof |
US20020045678A1 (en) * | 2000-08-22 | 2002-04-18 | Lopez Larry A. | Dental restorative compositions and method of use thereof |
US6815470B2 (en) * | 2000-09-26 | 2004-11-09 | Tokuyama Corporation | Dental catalyst for chemical polymerization and use thereof |
US6759449B2 (en) * | 2000-11-28 | 2004-07-06 | Tokuyama Dental Corporation | Dental adhesive composition |
US6653365B2 (en) * | 2001-05-01 | 2003-11-25 | Pentron Clinical Technologies, Llc | Dental composite materials and method of manufacture thereof |
US20050038135A1 (en) * | 2001-05-01 | 2005-02-17 | Shuhua Jin | Dental composite materials and method of manufacture thereof |
US20030207960A1 (en) * | 2001-05-10 | 2003-11-06 | Weitao Jia | Self-etching primer adhesive and method of use therefor |
US20040156795A1 (en) * | 2001-07-09 | 2004-08-12 | Kimiya Nemoto | Dental self-etching primer |
US20030055124A1 (en) * | 2001-08-10 | 2003-03-20 | Klee Joachim E. | Hydrolysis stable one-part self-etching, self-priming dental adhesive |
US20030125444A1 (en) * | 2001-11-02 | 2003-07-03 | Weitao Jia | Dental resin materials, method of manufacture, and uses thereof |
US6649669B2 (en) * | 2001-12-28 | 2003-11-18 | American Dental Association Health Foundation | Single solution bonding formulation |
US20030175659A1 (en) * | 2002-02-07 | 2003-09-18 | Amer Tiba | Multifunctional dentin bonding agent |
US6673958B2 (en) * | 2002-02-07 | 2004-01-06 | Bisco, Inc. | Multifunctional dentin bonding agent |
US20070299157A1 (en) * | 2003-05-13 | 2007-12-27 | Junjie Sang | Dental adhesive compositions and methods |
US20040229973A1 (en) * | 2003-05-13 | 2004-11-18 | Junjie Sang | Dental adhesive compositions and methods |
US20040235981A1 (en) * | 2003-05-19 | 2004-11-25 | Kerr Corporation | Two-part self-adhering dental compositions |
US20050020720A1 (en) * | 2003-07-02 | 2005-01-27 | Ada Foundation | Remineralizing dental cements |
US20050014861A1 (en) * | 2003-07-17 | 2005-01-20 | Kerr Corporations | Methods of using two-part self-adhering dental compositions |
US20050049326A1 (en) * | 2003-08-29 | 2005-03-03 | Park Kwang Soo | Dental self-curing resin cement compositions |
US20050277706A1 (en) * | 2004-06-09 | 2005-12-15 | Han Dong K | Highly functional dental adhesive composition |
US20070197683A1 (en) * | 2006-02-23 | 2007-08-23 | Pentron Clinical Technologies, Inc | Self etch all purpose dental compositions, method of manufacture, and method of use thereof |
US20070197682A1 (en) * | 2006-02-23 | 2007-08-23 | Weitao Jia | Self etch all purpose dental cement composition, method of manufacture, and method of use thereof |
US20080242761A1 (en) * | 2006-02-23 | 2008-10-02 | Weitao Jia | Self etch all purpose dental compositions, method of manufacture, and method of use thereof |
Cited By (22)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20060270752A1 (en) * | 2005-05-26 | 2006-11-30 | Ada Foundation | Dental releasing materials |
US20070049656A1 (en) * | 2005-09-01 | 2007-03-01 | Pentron Clinical Technologies, Inc | Dental resin composition, method of manufacture, and method of use thereof |
US7855242B2 (en) | 2005-09-01 | 2010-12-21 | Pentron Clinical Technologies Llc | Dental resin composition, method of manufacture, and method of use thereof |
WO2007100569A2 (en) * | 2006-02-23 | 2007-09-07 | Pentron Clinical Technologies Llc | Self etch all purpose dental composition |
US8664294B2 (en) | 2006-02-23 | 2014-03-04 | Pentron Clinical Technologies, Llc | Self etch all purpose dental cement composition and method of use thereof |
WO2007100569A3 (en) * | 2006-02-23 | 2008-05-22 | Pentron Clinical Technologies | Self etch all purpose dental composition |
US20080242761A1 (en) * | 2006-02-23 | 2008-10-02 | Weitao Jia | Self etch all purpose dental compositions, method of manufacture, and method of use thereof |
JP2009527561A (en) * | 2006-02-23 | 2009-07-30 | ペントロン クリニカル テクノロジーズ リミテッド ライアビリティ カンパニー | Self-etching universal dental composition, method for producing the same, and method for using the same |
US20070197683A1 (en) * | 2006-02-23 | 2007-08-23 | Pentron Clinical Technologies, Inc | Self etch all purpose dental compositions, method of manufacture, and method of use thereof |
US20070197682A1 (en) * | 2006-02-23 | 2007-08-23 | Weitao Jia | Self etch all purpose dental cement composition, method of manufacture, and method of use thereof |
US7906564B2 (en) | 2006-02-23 | 2011-03-15 | Pentron Clinical Technologies, Llc | Self etch all purpose dental cement composition, method of manufacture, and method of use thereof |
US20110171608A1 (en) * | 2006-02-23 | 2011-07-14 | Pentron Clinical Technologies, L.L.C. | Self etch all purpose dental cement composition and method of use thereof |
US20080286724A1 (en) * | 2007-05-18 | 2008-11-20 | Ormco Corporation | Orthodontic adhesives |
US9408782B2 (en) | 2007-05-18 | 2016-08-09 | Ormco Corporation | Orthodontic adhesives |
EP1992321A3 (en) * | 2007-05-18 | 2010-10-13 | Ormco Corporation | Orthodontic adhesives |
US8821157B2 (en) | 2007-05-18 | 2014-09-02 | Ormco Corporation | Orthodontic adhesives |
US20100240794A1 (en) * | 2009-03-20 | 2010-09-23 | Shuhua Jin | Dental resin composition, method of manufacture, and method of use thereof |
US8163815B2 (en) | 2009-03-20 | 2012-04-24 | Pentron Clinical Technologies, Llc | Dental resin composition, method of manufacture, and method of use thereof |
EP2230286A1 (en) * | 2009-03-20 | 2010-09-22 | Pentron Clinical Technologies, LLC | Dental resin composition, method of manufacture, and method uf use thereof |
US8053490B2 (en) | 2009-05-18 | 2011-11-08 | Pentron Clinical Technologies, Llc | Pre-treated acid-reactive fillers and their use in dental applications |
US20160045403A1 (en) * | 2013-03-15 | 2016-02-18 | The Regents Of The University Of California | Calcium sulfate-resin hybrid materials and methods of using and making the same |
US9889071B2 (en) * | 2013-03-15 | 2018-02-13 | The Regents Of The University Of California | Calcium sulfate-resin hybrid materials and methods of using and making the same |
Also Published As
Publication number | Publication date |
---|---|
US7700667B2 (en) | 2010-04-20 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US7632877B2 (en) | Dental resins, dental composite materials, and method of manufacture thereof | |
US7700667B2 (en) | Dental resin composition, method of manufacture, and method of use thereof | |
US6653365B2 (en) | Dental composite materials and method of manufacture thereof | |
US7906564B2 (en) | Self etch all purpose dental cement composition, method of manufacture, and method of use thereof | |
US6730715B2 (en) | Dental restorative composition, dental restoration, and a method of use thereof | |
US7855242B2 (en) | Dental resin composition, method of manufacture, and method of use thereof | |
US7470728B2 (en) | Dental glazes and method of manufacture and use thereof | |
US7589132B2 (en) | Dental resins, dental composite materials, and method of manufacture thereof | |
US20020045678A1 (en) | Dental restorative compositions and method of use thereof | |
JP4986437B2 (en) | Dental curable composition | |
US7160941B2 (en) | Dental composite materials and method of manufacture thereof | |
US20050124762A1 (en) | Dental compositions containing core-shell polymers with low modulus cores | |
JP4425568B2 (en) | Dental composition | |
US20080242761A1 (en) | Self etch all purpose dental compositions, method of manufacture, and method of use thereof | |
US6767955B2 (en) | Flowable dental resin materials and method of use thereof | |
US8163815B2 (en) | Dental resin composition, method of manufacture, and method of use thereof | |
US20130023600A1 (en) | Dental compositions containing short-cut fibers | |
US4420306A (en) | Tetraacrylic and tetramethacrylic esters and dental materials containing same | |
WO2002015848A2 (en) | Dental restorative compositions and method of use thereof | |
US8664294B2 (en) | Self etch all purpose dental cement composition and method of use thereof | |
US20050124722A1 (en) | Branched highly-functional monomers exhibiting low polymerization shrinkage | |
JP3409291B2 (en) | Amine-based unsaturated compound and photocurable composition containing the same | |
US20070015845A1 (en) | Dental resin composition, method of manufacture, and method of use thereof | |
WO2023042715A1 (en) | (meth)acrylamide compound, monomer composition, composition for dental material, and dental material | |
JP2023095695A (en) | dental adhesive kit |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AS | Assignment |
Owner name: PENTRON CLINICAL TECHNOLOGIES, LLC,CONNECTICUT Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:JIN, SHUHUA;JIA, WEITAO;REEL/FRAME:016320/0855 Effective date: 20050526 Owner name: PENTRON CLINICAL TECHNOLOGIES, LLC, CONNECTICUT Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:JIN, SHUHUA;JIA, WEITAO;REEL/FRAME:016320/0855 Effective date: 20050526 |
|
STCF | Information on status: patent grant |
Free format text: PATENTED CASE |
|
FPAY | Fee payment |
Year of fee payment: 4 |
|
MAFP | Maintenance fee payment |
Free format text: PAYMENT OF MAINTENANCE FEE, 8TH YEAR, LARGE ENTITY (ORIGINAL EVENT CODE: M1552) Year of fee payment: 8 |
|
AS | Assignment |
Owner name: BANK OF AMERICA, N.A., AS ADMINISTRATIVE AGENT, NORTH CAROLINA Free format text: SECURITY INTEREST;ASSIGNOR:KERR CORPORATION;REEL/FRAME:052611/0362 Effective date: 20200506 |
|
AS | Assignment |
Owner name: KERR CORPORATION, CALIFORNIA Free format text: RELEASE BY SECURED PARTY;ASSIGNOR:BANK OF AMERICA, N.A., AS ADMINISTRATIVE AGENT;REEL/FRAME:055886/0185 Effective date: 20210408 |
|
MAFP | Maintenance fee payment |
Free format text: PAYMENT OF MAINTENANCE FEE, 12TH YEAR, LARGE ENTITY (ORIGINAL EVENT CODE: M1553); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY Year of fee payment: 12 |